Extraction of hydrocarbon products from shales and coals.



c CI Patented Oct. 30, 1917.

` APPLICATION FILED nec. I. I9I6.

EXTRACTION 0F HYDROCAIRBON PRODUCTS FROM 'SHALES AND GOALS..

sra'rns PATENT OFFICE.

DAVIDE, DAY, or WASHINGTN, DIsTnIc'r oF coLnMBIA, AssIGNon. :so VEBNERz,

- REED, 0F DENVER, COLORADO.

ExTaAcTIoN or HYDRooARBoN rRoDUcrsritoiy/r sHALns'AND coALs.

To all whom z't may concern.' A

Be it known that I, DAVID'T. DA1, a citizen of the United States,residing at Washington, in the District of Columbia, have invented newand useful Improvements in the Extraction of Hydrocarbon Products fromShales and Goals, of which the following is a specification.

This invention relates to improvements in the extraction of hydrocarbonproducts, nitrogen bases, oils and the like from shales and coals.

One feature of the invention pertains to the combined extraction ofmaterial by` vsolvent action and destructive distillation.

A further feature of the invention includes the use of vapors derivedfrom the shale as a novel solvent for the volatile matter present insuch shale or coal.

In the ordinary process of obtaining oils and other hydrocarbonproducts, nitrogen bases, and the like, from shales, and in somev casesfrom coals, it is customary to heat these shales in'stills Withoutaccess of air. Usually vertical stills are employed, the shale beingintroduced at the top, and after its introduction, the top is closedwith a bell hopper or other device.l Heat is vapplied around this stillso that it is hotter.' at the bottom and the vapors are driven 0Ethrough an exit pipe somewhere near the top. Frequently steam isintroduced near the bottom of the still forv the purpose of breaking uphighly resistant compounds,- and especially in increasing the formationof ammonia as a valuable by-product. In other cases, screw or endlesschain conveyers are used for carrying the shale through hot tubes, thevapors being taken off at the upperor lower end of the heated tube. Ineach instance the proiit in operating such a still increases with theamount of volatile material which can be driven OE from the shale, andon the other hand the profit ceases when the shales yield such a smallproportion of oils, and the like, that they yield less v in value thanthe combined comparatively high cost of heating the body of shale andcost of furnishing heat for the evaporation of the volatile matter. Theheat required is greater than inthe distillation of oils, for

-besides the quantity consumed in the distillation of alreadyexistingloil in the shaleis that heat needed for the high temperatureSpecification of Letters Patent. Patenfgd 001;, 30, 1917-, Applicationilled December 1, 1916. Serial No. 184,470. l l

required for the destructive distillation of the organic matter in theshalel It is well known that many shales contain considerable oilalready existing as oil,

which is shown by the fact that this oil can be extracted bysuitable.solvents such as ether, benzol and other lightaromatic soils, gasolene,phenol, etc. In some cases I have obtained as much 'as three' fths ofthe oil obtainable by distillation, by simple extraction with a hotsolvent. A process, however, based merely on extraction by solventswould be costly, and would also leave val- '.uable volatile productsstill present in the shale, especially nitrogen .bases and other'destructive distillation' at high tempera` tures, and therefore at highcost.

In this process a certain amount of the shale is first introduced fromthe extraction chamber described hereafter into an inclined, tubularretort, which is then vsubjected to the temperature necessary to driveout all of the volatile matter. This volatile matter is then deliveredin the. form of vapor, or

vapor andV liquid, intoan extraction chamber containing the shale to beheated. These vapors condense to a certain extent in the Y chamber ofcold shale and the hot condensed liquids lexert the maximum solventaction possible and thereby take out of the shalev a large proportion ofthe contained volatile materials.

through ,the shale Will enter the pores of the shale and combine withthe oil therein renderingthis oil thinner andv give ita tendency 'toflow out of the shale. The resulting liquid is drawn olf at the bottomoffthis chamber and thev shale, thus partially deprived' of fits'volatile matter andliquid, is delivered through the bottom of theshale-holding chamber on to a screw or'otherfconveyer'by "which it isdeliveredinto therstmentionsd fhttube or retort whereLth'eremainmg"velas` tilefmatter is`extracted"byl'destruztive distilla'tion. Theresultingvapors ar'efcontilr-V Some of the vapor in passing uallydelivered into'the shalefor-:tankl and continuallyneireit atip'li.'onneW This process presents the use 'of the va pors from the: shaleitself as a new solvent for the volatile' 'matter in'. such shale. Ithas been found that much of lthe hydrocarf bon material present inshales is adsorbed to the surfaces'of the shale particles and when thevolatile matter 'the :chamber- 1 for 'substances such as acids, assolvents7 .preventing permeates the shaleinsuch a Way as to be insolubleuntil acted upon by acid or basic phenols, pyroligneous acid or basicsubstances, becomes soluble in benzol or other aromatic hydrocarbons orgasolene containing phenols. The present process eliminates muchexpensive treat# ment by 'providing for the use of said solvents founddirectly in the condensed vapors from the shale itself.. The inventionalso provides the useof acids, including mineral without regard to theirand the invention is not limited to acid, pyridins, and

origin, their production shale.

In the operation. ofthe invention, the

process may be carried out by. means of the apparatus illustrated 'inthe accompanying drawing..

The figure represents in elevation a suit- 'abl'e apparatus 1n which toexecute the proccss. In the'drawing lindicates an extraction chamber inwhich fresh cold shale is subjected tothe solvent action of vapors asvrwill be further described. Located above. the chamber 1 is 'areceiving hopper 2 ar. ranged to receive material such as shale or.

coal .broughtthereto by means of suitable conveyer app' aratus indicatedby A3. Closures are provided'at the Atop and bottom of` limiting thepassage of' shale intofand out of a chamber and'also for "from thechamber While the shale is being treated. Located adjacent the top ofthe chamber 1 is av conduit 4 leadingoff 4from the chamber and designedto provide a passageway for the discharge of lgasesto a condenser andscrubber, not shown. Adjacent the base of the chamber 1 there is aconduit for conducting the extracted liquids'and condensed vapors toasuitable vtank for storage. numeral 5. At the junction of the conduit'with the chamber 1 there is provided suitablem'eans for preventing theshale material into the conduitas 1nd1- cated by a slottedV screen 6 and,a wire screen of Wovenfmaterial 7. The'conduit 5 isprovided with agooseneclrbend toprovide' a such apparatus. At'theb'aseof the'l'mm.

` further described.

by distillation 'from the` indicated at the -escape of the solventvapors. Athis being effected by This conduit is indicated: by 'the theI:discharge of 'chamber 1- ber lfprovisio'n is made forthe discharge ofthe shale into' the inclined tubular retort 8 which is provided with ascrew conveyer arranged te carry material through they same.

'Thisl tubular'retort 8 is provided with a heating device or 'furnace asindicated by 9 Ichamber 1 is a discharge passage for 'the spent shaleindicated by 11. At the oppo-. site end from the discharge passage 11and somewhat nearer the chamber 1, vthe tube 8 is provided with adischarge passage 12 for the vapors extracted from the shale in the-tube 8. These vapors `are carried from the tube 8, throughthe dischargepassage 12 and into a .passageway 13- from which they. are conducted asvapors to the top of thechamber 1 by means of the conduit la'sfwiilll-beHeavy matters" such' as tar which may be liberated in the tube 8 andpassed through the discharge passage 12 andpassageway l'may be trappedadjacent the bottom of the member 13 and led toa receiving tank for tar.as indicated by the passageway 15. An optional 'treatmentvis provided bythe conduit, 16 through which the heavy tars may b e delivered forcracking A by the hot spent shale discharged through the passage 17 isan inlet passage fonsupe? 11. GonnectedIto the systemes u heated steamfor use if it be desirabletp i.;.

use steam in the extraction process. A steam generator is showndiagrammatically at 18 ,a 'superheater therefor at .19v and a pressuregageat 20.

In the operation of the process andithe' apparatus an amount ofshaleJis-introdueed from the chamber 1 into theftubular'i'etort 8 Whereit is subjected=to atemperatre necessary to drive out lall Vvolz'rt-ilematter,

the heat 0f the furnace 9. The volatile matter isthen deliv ered in theform of a vapor'or a vaporfa'nd liquid through the passageways 12,13;and 14 into the chamber 1 containing 'thld shale to be treated. Thehotsvaporsgoondense to a certain extent inthe chamber of cold-shale andthe hot condensed-liquids exert the maximum solvent action possible andthereby take out of the shale a large proportion of the volatilematerials contained therein. The resulting extracted liquid containingthe material previously adsorbed to the' shale particles is drawn olffromi'the -I by- -the lconduit 5. The shale .whichhas been deprivedl of`its volatile mat ter is delivered `from the chamber -1' into the tube8and conveyed'by means of. the screwv conveyer into that-portion of thetube heat# ed by the 'furnace-9 I.:-.[,1ethel remaining lvolatile matteris extracted by destructive.

distillation and the resulting vapors containing phenols, pyridins, andacids are continuously delivered through the passageway 12, 13 and V14into the top of the chamber 1 as previously described where these vaporsexercise their solvent action on new portionsv of shale which may be ledinto the cham- Aber 1. 1

From the foregoing it will be obvious that this process provides meanswhereby oils and other hydrocarbon products may be 1. The process oftreating shales or coals i to extract volatile matters present in suchshalesv or coals which consists in subjecting such shale or coal in onechamber to destructive distillation, condensing the vapors so generatedin a mass of `similar shale or coal in a second chamber to dissolvematerial from said shale'or coal, and separatlng the combmed condensedvapor and material dissolved'thereby from the particles,

of shale or coal.

f 2. The process of treating shales or coals to extract hydrocarbonlmaterial therefrom which comprises the extraction in one chamber ofsolvent material from said shale or coal by the destructive distillationof a portion of semi-spent shale or coal, the application in asecondchamber of the hot extracted material to a mass of substantiallyuntreated shale whereby said hot extracted material dissolveshydrocarbon matter from said shale and the recovery of the combinedcondensed solvent and extracted matter in liquid form from said mass ofsemispent shale or coal.

3. The` continuous process of treating l shales or coals to extracthydrocarbon material therefrom which comprises iirst the extraction inone chamber of a vapor from said shale or coal by the destructivedistillation of a portion of semi-spent shale or coal,

the application in a second chamber of the hot extracted vaporousmaterial to a mass of substantially untreated material whereby said hotextracted material dissolves hydrocarbon matter from said untreatedmaterial, the recovery of the combined condensed solvent and extractedmatter in liquid form from said mass of untreated material which therebybecomes semi-spent material, and the. subsequent primary treatment ofsaid semi-spent material to obtain vapors therefrom by destructivedistillation.

4. The process of treating shales or coals `to extract hydrocarbonmaterial therefrom which comprises the extraction in one chamber ofvaporous materlal containmg pyridins from said shale orcoal by thedestructive .A

. extraction in one chamber of a vapor containing pyridins from saidshale or coal by the destructive distillation of a portion of semi-spentshale or coal, the application in a second chamber of thehot extractedmaterial to a mass of substantially untreated material whereby said hotextracted'material containing pyridins condenses and dissolveshydrocarbon matter from said untreated material, the recovery of thecombined condensed solvent and extracted matter in liquid form from saidmass of untreated material which thereby becomes semi-spent material,and the subsequent primary treatment in said first chamber of saidsemispent material to obtain vapors therefrom by destructivedistillation.

6. The process of extracting hydrocarbon matter from shales and coalswhich com-v prisesv subjecting a mass of such shale or coal containingthe desired hydrocarbon matter in a container to the action of hotvaporous material, condensing said vaporous material in said shale orcoal, permitting the condensed materials to pass downwardly through themass of shale or coal and exercise a solvent action on the oil materialtherein, and recovering the combined solvent and extracted matter.

7 The process of extractin hydrocarbon matter from shales and coa swhich comprises subjecting a mass of such shale or coal containing the4desired hydrocarbon matter ina container to the action of' hot vaporousmaterial containing pyridins, condensing said vaporous material in saidshale or coal, permitting the condensed materials to pass downwardlythrough the mass lof shale or coal and exercise a solvent action on theoil materialtherein, and recovering the combinedsolvent and extractedmatter.

In testimony 4whereof I have hereunto set my hand in presence of twosubscribing witnesses.

DAVID T. DAY.

